pubs.acs.

org/acscatalysis Research Article

Low-Coordination Rhodium Catalysts for an Efficient

Electrochemical Nitrate Reduction to Ammonia
Huimin Liu, Janis Timoshenko, Lichen Bai, Qinye Li, Martina Rüscher, Chenghua Sun,
Beatriz Roldan Cuenya, and Jingshan Luo*
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ABSTRACT: Ammonia is an essential bulk chemical and the main

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component of fertilizers. In addition, the use of ammonia (NH3) as

an energy carrier and hydrogen storage material has continuously
surged. Electrochemical nitrate reduction is a low-carbon, environ-
ment-friendly, and efficient method of ammonia synthesis, which has
attracted extensive attention in recent years; however, the over-
potential needed to produce NH3 with most catalysts is still too large.
In this work, we rationally designed rhodium nanoflowers (Rh NFs)
composed of ultrathin nanosheets and explored their performance for
the electrocatalytic nitrate reduction to ammonia (NITRR). With a
high faradic efficiency of 95% at 0.2 V vs reversible hydrogen
electrode (RHE) for ammonia production, the overpotential required
for the NH3 formation on an Rh NF catalyst is much lower than on
most previously reported catalysts. X-ray absorption spectroscopy (XAS) analysis shows that there are low-coordination atoms in the
Rh NF catalyst, which can promote the adsorption of NO3− ions and stabilize intermediates as revealed by the density functional
theory (DFT) calculation, resulting in efficient NITRR performance.
KEYWORDS: electrocatalysis, nitrate reduction, ammonia synthesis, low-coordination catalyst, rhodium

■ INTRODUCTION
Ammonia is one of the chemicals with the highest fabrication
electrochemical nitrogen reduction for ammonia synthesis;
therefore, it has become a hot topic in the field of
output in the world, and its market size and value account for electrocatalysis. From the environmental perspective, more-
over, large amounts of nitrate are produced every year due to
5% of the global chemical market value. At present, 80% of the
the excessive use of chemical fertilizer,6 which leads to serious
produced ammonia is used for the production of chemical
water eutrophication, resulting in diseases such as methemo-
fertilizers for agricultural use. Ammonia is also the raw material
globinemia and non-Hodgkin’s lymphoma.7 Therefore, the
for explosives, drugs, refrigerants, and textiles. Therefore,
degradation of nitrate into valuable ammonia has great
ammonia plays a crucial role in human life, survival, and
prospects and significance in maintaining the balance of
development.1 Research on renewable energy in the past
nitrogen species in nature so as to not endanger human
decade shows that the large-scale transportation of renewable
health.2
energy from areas rich in solar radiation resources and wind to
Electrocatalytic nitrate reduction can occur at the solid−
the destination market is still a major obstacle and a
liquid interface with a low reaction barrier,8 and its kinetics can
bottleneck. Due to the high energy density and hydrogen
be optimized relative to the competitive hydrogen evolution
content, easy liquefaction, storage, and transportation,
reaction (HER).9−13 However, most nitrate reduction to
ammonia has emerged as an increasingly compelling candidate
ammonia (NITRR) electrocatalysts still suffer from the low
to be used as a carbon-free and renewable energy carrier.2
energy efficiency caused by the high overpotential required and
However, at present, the main pathway for industrial
low faradic efficiency (FE) caused by the competing HER. A
ammonia synthesis is still the Harber−Bosch (H−B) process,
which consumes a lot of energy and emits a large amount of
greenhouse gas CO2.3−5 Therefore, it is urgent to develop Received: June 22, 2022
green and sustainable ammonia synthesis methods. In recent Revised: December 13, 2022
years, with the development of electrochemical nitrogen Published: January 10, 2023
oxidation and plasma nitrogen oxidation methods, the strategy
of first oxidizing nitrogen to NOx or NO3− and then reducing
them to ammonia has become more feasible than the direct

© 2023 American Chemical Society https://doi.org/10.1021/acscatal.2c03004

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Figure 1. Characterization of Rh NFs and Rh NPs. X-ray diffraction (XRD) pattern of (a) Rh NFs and (c) Rh NPs. X-ray photoelectron
spectroscopy (XPS) of (b) Rh NFs and (d) Rh NPs. (e, f) Scanning electron microscopy (SEM) image, (g) high angle annular dark field scanning
transmission electron microscopy (HAADF-STEM) image, (h) transmission electron microscopy (TEM), and (i) high-resolution transmission
electron microscopy (HRTEM) image of Rh NFs. (j, k) SEM, (l) HAADF-STEM, (m) TEM, and (n) HRTEM images of Rh NPs.

recent theoretical study of activity trends in the electrocatalytic

nitrate reduction on transition metals shows that Rh has the
■ RESULTS AND DISCUSSION
Catalyst Preparation and Characterization. Rh NFs
highest activity at positive potentials (ca. 0−0.4 V vs reversible and Rh NPs were prepared by reducing rhodium acetylacetone
hydrogen electrode (RHE)) because of its moderate nitrate and rhodium chloride precursors with formaldehyde without
and hydrogen adsorption energies.14 However, due to the surfactant, respectively.21,22 The characterizations of Rh NFs
rareness and high price of Rh, there is a strong demand to and Rh NPs catalysts are illustrated in Figure 1. The X-ray
reduce the amount of Rh in the electrode in use without diffraction (XRD) peaks at 2θ of 40.7, 47.7, and 69.8°
sacrificing its activity. Benefitting from the fascinating proper- correspond to the (111), (200), and (220) facets of Rh,
ties such as high atom utilization efficiency, high electron respectively, which prove that Rh NFs and Rh NPs catalysts
mobility, tailored electronic structures, and abundant low- are in the metallic state and their main crystal plane is (111)
coordination atoms as active sites, ultrathin two-dimensional (Figure 1a,c). Meanwhile, the broad full width at half-
nanomaterials show promise for electrocatalytic applica- maximum of the (111) diffraction peak in Rh NFs reveals
tions.15−20 that the average thickness of ultrathin nanosheets in Rh NFs is
Based on the high activity of Rh for electrocatalytic nitrate smaller than the average size of Rh NPs according to the
reduction, the unique properties of two-dimensional materials, Scherrer formula.23 The corresponding energy-dispersive X-ray
and the need to improve atom utilization of precious metals, spectroscopy (EDS) results show a strong Rh signal and a
herein we rationally designed rhodium nanoflowers (Rh NFs) weak O signal due to unavoidable surface oxidation in both Rh
composed of ultrathin nanosheets for the NITRR. A high NFs and Rh NPs (Figure S1), as corroborated by X-ray
photoelectron spectroscopy (XPS) survey scan results (Figure
faradic efficiency of 95% at 0.2 V vs RHE was achieved on Rh
S2). The high-resolution Rh 3d spectrum (Figure 1b,d) mainly
NFs, which is much higher than that for the Rh nanoparticles consists of two group peaks, corresponding to Rh0 (307.2,
(Rh NPs), and the required overpotential is much lower than 312.0 eV) and oxidized Rh (308.8, 313.5 eV) species.24 It is
those for most of the currently reported catalysts. An in-depth worth noting that the Rh NFs with an ultrathin two-
X-ray absorption spectroscopy (XAS) analysis shows abundant dimensional structure have a positive binding energy shift of
low-coordination Rh atoms in the Rh NFs. The density 0.5 eV compared to Rh NPs and the standard signal of Rh0,
functional theory (DFT) calculation indicated that low- which is related to the unique electronic structure of the two-
coordination Rh can promote NITRR, including enhanced dimensional material with atomic thickness.25
adsorption of NO3− ions and better stabilization of reaction The scanning electron microscopy (SEM) and transmission
intermediates. electron microscopy (TEM) images reveal an ultrathin
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Figure 2. (a) Linear sweep voltammogram (LSV) curves of Rh NFs in 0.1 M Na2SO4 electrolyte (pH 11.5) in the presence (red) and absence
(gray) of 0.1 M NO3−. The potential range is between 0.3 and −0.50 V vs RHE, and the scan rate is 5 mV s−1. (b) Ammonia yield rate and faradic
efficiency of Rh NFs for NITRR. (c) Faradic efficiency of Rh NFs and Rh NPs for the electrocatalytic nitrate reduction to ammonia (NITRR) at
each potential in the 0.1 M Na2SO4 (pH 11.5) electrolyte containing 0.1 M NO3−. (d) Partial current density of ammonia production at each
potential for Rh NFs and Rh NPs for NITRR. (e) Current density and faradic efficiency of ammonia production when NITRR was catalyzed by Rh
NFs for 10 cycles (1 h per cycle) at an applied potential of 0.2 V vs RHE. The electrolyte was exchanged every hour. (f) Faradic efficiency and
ammonia production of Rh NFs for NITRR in the 0.1 M Na2SO4 electrolyte (pH 11.5) containing 5, 10, 100, 200, 1000, and 2000 mM NO3−,
respectively.

nanosheet-assembled nanoflower structure of Rh NFs with a S6 and S7). Both the yield rate and the partial current density
diameter of 200 nm (Figure 1e−h). The size of each nanosheet of ammonia for Rh NFs have far outperformed those for Rh
is about 100 nm and its thickness is about 1 nm according to NPs (Figures 2d and S3), indicating the superior performance
the previous report.21 Similar characterizations of Rh NPs used of Rh NFs for the NITRR.
for control experiments show that uniformly dispersed Rh NPs When the NITRR was conducted under 0.2 V vs RHE over
are composed of ca. 30−50 nm smaller Rh grains (Figure 1j− Rh NFs for 10 cycles and the electrolyte was exchanged every
m). The high-resolution TEM images in Figure 1i,n show the hour, there was no notable attenuation in faradic efficiency
lattice spacings of Rh NFs and Rh NPs, which are determined (Figure 2e). A rapid decrease in the current density at the
to be 0.22 nm, corresponding to the Rh (111) facet. initial stage of each cycle might be attributed to the double
Activity and Selectivity for NITRR to Ammonia. We layer rearrangement26 and the accumulation of adsorbed N
first collected the linear sweep voltammogram (LSV) curves of species on the surface of the catalyst over time, which blocks
Rh NFs and Rh NPs in Ar-saturated 0.1 M Na2SO4 (pH 11.5) the active sites, and consequently the overall electrochemical
electrolyte (Figures 2a and S3). Between 0.3 and −0.10 V vs nitrate reduction rate is decreased. Nevertheless, the current
RHE, a significant current density increase of Rh NFs in the can be recovered in the next cycle, indicating the excellent
presence of nitrate compared to the absence of nitrate electrochemical stability of the Rh NFs. Furthermore, the Rh
preliminarily indicates that it is active in nitrate reduction.8 NFs after electrocatalysis show intact morphology and
Subsequently, the determination of the NITRR product for structure, proving their structural stability for the NITRR
Rh NFs and Rh NPs at different potentials shows that the (Figures S8 and S9). When the added NO3− concentration is
highest faradic efficiency for the NH3 production (95%) on Rh reduced to 10 and 5 mM, the FE for NH3 of Rh NFs also
NFs is much higher than for Rh NPs (60%) (Figures 2b,c, S3, decreases. When the NO3− concentration is increased to 200,
and S4). It is worth noting that the optimal potential (0.2 V vs 1000, and 2000 mM, the ammonia yield rate increases with the
RHE) of Rh NFs for NITRR is among the highest reported NO3− concentration and the FE remains above 90%, indicating
potentials (least overpotential) (Figure S5 and Table S1), that high NO3− concentrations are applicative for Rh NFs to
indicating that a reduced overpotential is achieved and the catalyze NITRR (Figures 2f and S10).
competing HER can be avoided. Below 0 V vs RHE, the FE of To verify the origin of the produced NH3 and the accuracy
ammonia production decreases. The FE of H2 formation of ammonia detection, we conducted a series of control
accounts for 55% at −0.1 V vs RHE, which is caused by strong experiments and 1H nuclear magnetic resonance (NMR)
hydrogen evolution competition. The FE of nitrite quantified experiments to detect the generated NH3 on Rh NFs in an
by colorimetric detection is low at various potentials (Figures electrolyte containing 0.1 M 15N-labeled 15NO3− or 14N-
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Figure 3. (a) Ammonia yield of Rh NFs after NITRR in the 0.1 M Na2SO4 (pH 11.5) electrolyte containing 0.1 M KNO3 at 0.2 V vs RHE. The
ammonia yield of Rh NFs after the control experiment in the 0.1 M Na2SO4 (pH 11.5) electrolyte at 0.2 V vs RHE; ammonia yield of Rh NFs after
the control experiment in the 0.1 M Na2SO4 (pH 11.5) electrolyte containing 0.1 M KNO3 without an applied potential. (b) 1H nuclear magnetic
resonance (NMR) spectrum of the electrolyte after NITRR on Rh NFs at 0.1 V vs RHE with 15NO3− and 14NO3− as nitrogen sources. (c) After
NITRR on Rh NFs at 0.1 V vs RHE with 15NO3− and 14NO3− as nitrogen sources, the faradic efficiency is calculated by the indophenol method
and NMR spectroscopy, respectively. Electrochemical active surface area (ECSA) of (d) Rh NFs and (e) Rh NPs. (f) Partial current density of
ammonia production normalized to ECSA of Rh NFs and Rh NPs for NITRR.

labeled 14NO3−. In the absence of nitrate or without the is negligible, nor does it affect the ECSA of Rh catalysts. After
applied potential, the NH3 yield of Rh NFs was lower than the being normalized to the ECSA, the partial current density of
detection limit (Figure 3a). Furthermore, after isotope labeling ammonia production over Rh NFs is still higher than that of
experiments, the 14NH3 FE quantified by the triple peak and Rh NPs, which proves the superior intrinsic activity of Rh NFs
the 15NH3 FE quantified by the bimodal coupling for 1H NMR with respect to Rh NPs (Figure 3f). To check whether the use
are very close (Figures 3b,c and S11) and also consistent with of a Cl− precursor in the synthesis of the Rh NPs influences
the quantitative results by indophenol method (Figures 3c and our results, we carried out several control experiments. First,
S12−S14). These results directly prove that the detected our XPS (Figure S2) analysis did not show the presence of Cl
ammonia is only derived from the reduction of nitrate rather in Rh NPs after the repeated washing step during the synthesis
than any contamination and guarantee the accuracy of the process. Furthermore, our results showed that the ammonia
indophenol method mainly applied in this work. yield rate and FE of Rh NFs did not change in the presence of
Study of the Mechanism. To derive the origin of the high 0.01 M Cl− (Figure S17). Therefore, we could exclude the
NITRR activity for Rh NFs, its catalytic mechanism was possibility that the superior performance of Rh NFs compared
explored. First, as the Rh NFs are a three-dimensional to the Rh NPs is derived from the presence of Cl− poisoning in
nanosheet assembly, it can be reasonably assumed that the Rh NPs.11,27
reactants can more easily reach the active sites of the Rh NFs We used operando X-ray absorption spectroscopy (XAS), in
due to their larger surface-to-volume ratio than in the case of particular, X-ray absorption near edge structure (XANES) and
Rh NPs. The electrochemical active surface area (ECSA) was extended X-ray absorption fine structure (EXAFS) analysis, to
measured and calculated by cyclic voltammetry (CV) sweeps investigate the differences in the structure of Rh NPs and Rh
at different scan rates (Figures 3d,e and S15). The ECSA of Rh NFs under NO3− reduction reaction conditions. The collected
NFs is 332.5 cm2, which is higher than that of Rh NPs (169.0 Rh K-edge XANES spectra for both catalysts and reference
cm2). Cyclic voltammetry (CV) control measurements of samples are shown in Figure 4a,d. All of the spectra lie in
carbon cloth substrates at different scan rates show that its between those for Rh foil and Rh2O3, suggesting that Rh is
current density is about 2 orders of magnitude lower than that partially oxidized. The fraction of oxide, however, is different
of Rh NFs or Rh NPs loaded on a carbon cloth electrode in the for Rh NPs and Rh NFs and changes under the applied
same test potential range (Figure S16). Therefore, the carbon potential. For Rh NPs, all of the spectra are closer to the
cloth substrate contribution to the CV of Rh NFs and Rh NPs spectra of Rh foil, suggesting that Rh is mostly in metallic form
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Figure 4. Rh K-edge X-ray absorption near edge structure (XANES) spectra for (a) Rh NFs and (d) Rh NPs. Spectra collected under OCP
conditions and under applied potential are compared. Rh K-edge extended X-ray absorption fine structure (EXAFS) spectra for (b) Rh NFs and
(e) Rh NPs. Fourier transform Rh K-edge EXAFS spectra for (c) Rh NFs and (f) Rh NPs. Spectra collected under OCP conditions and under
applied potential are compared. Reference spectra for Rh foil and Rh2O3 references are also shown.

(Figure 4d). For Rh NFs, XANES features more resemble the EXAFS spectra in k-space and Fourier transform EXAFS
spectrum of Rh2O3 compared to Rh NPs, suggesting the higher spectra for Rh catalysts are shown in Figure 4b,c.e,f,
content of oxide (Figure 4a). Upon exposure to NITRR respectively. In agreement with XANES results, the EXAFS
conditions, both for Rh NPs and Rh NFs, we observed a spectra for both catalysts exhibit clear similarity with that of Rh
reduction of oxide species, and the spectra became more like foil, suggesting a predominantly metallic structure of Rh NFs
that of Rh foil. Nonetheless, after exposure to 0.2 V vs RHE for and Rh NPs. We note that the frequency of EXAFS spectra in
30 min and then to −0.1 V vs RHE for 30 min, Rh in Rh NFs k-space (Figure 4b,e) matches well with that for Rh foil,
still contained some oxides. suggesting that Rh−Rh distances are very similar in the two
For more quantitative analysis, we performed linear samples and close to those in metallic Rh. Under reaction
combination analysis (LCA) of the collected Rh K-edge conditions and applied potential, the amplitude of the metallic
spectra. Figure S18 shows that all of the collected spectra can Rh features increases, while the amplitude of the peak in
indeed be reasonably expressed as linear combinations of the Fourier transformed (FT)-EXAFS, corresponding to the Rh−
spectra for Rh foil and Rh2O3. The weights of the Rh2O3 O bonds (peak at ca. 1.8 Å, phase uncorrected) decreases.
standard spectrum in the LCA fitting correspond to the Next, we fit the EXAFS spectra. The results of the fitting are
fraction of oxidized Rh and are summarized in Table S2. For summarized in Figure S21 and Table S3. All experimental
Rh NPs, the reduction is nearly complete under reaction spectra can be very well fitted with a combination of the Rh−O
conditions, for Rh NFs, ca. 21 and 16% oxidized Rh remained and Rh−Rh path contributions. In agreement with the results
in the sample after 30 min at 0.2 V vs RHE and another 30 min of the visual examination of EXAFS data, the Rh−O
at −0.1 V vs RHE, respectively. This does not rule out the contribution is much more pronounced for Rh NFs than
possibility that oxides may be further reduced for a longer time. that for the Rh NP sample, and in both cases, decreases under
However, the NITRR performance of Rh2O3 NFs prepared by the reaction conditions. Both Rh−O and Rh−Rh interatomic
the high-temperature calcination of Rh NFs in O2 was much distances match well those for Rh2O3 and Rh foil references.
lower than that of Rh NFs (Figures S19 and S20). Surprisingly, One can also note that disorder factors (σ2 factors) for Rh−Rh
the FE and ammonia yield rate of Rh2O3 NFs after bonds are larger in Rh NPs than in the Rh foil and are even
prereduction at −0.7 V vs RHE recovered to be close to Rh higher in Rh NFs. The increased structural disorder might be
NFs, proving that Rh0 was the main active site of NITRR over linked to the increased number of low-coordination metallic
Rh NFs. Rh sites. For the interpretation of the NRh−O and NRh−Rh
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Figure 5. (a) NH3 yield rate normalized to ECSA of Rh NPs and Rh NFs for NITRR in the 0.1 M Na2SO4 (pH 11.5) electrolyte containing 0.1 M
NO3− at 0.2 V vs RHE and 0.1 V vs RHE. Differential electrochemical mass spectrometry (DEMS) measurements of NITRR over (b) Rh NFs and
(c) Rh NPs. Computational investigation of Rh coordination number on catalyst performance. Free energy profiles of full NITRR over Rh with (d)
coordination numbers of 9 (Rh9C) and 5 (Rh5C) and (e) coordination numbers of 8 (Rh8C) and 7 (Rh7C) under external potential U = 0 V vs
CHE. Reaction coordinates are shown with surface adsorbents, starting with a clean surface, followed by NO3*, NO3H*, NO2*, NO2H*, NO*,
NOH*, N*, NH*, NH2*, and NH3*. Small molecules, protons, and electrons are not shown for clarity.

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coordination numbers (CN), as yielded by EXAFS fits for Rh

catalysts, the reduced Rh−Rh coordination numbers can be a
■ CONCLUSIONS
In conclusion, we designed Rh nanoflowers composed of
result of two effects: (i) coexistence of metallic Rh (with Rh− ultrathin nanosheets for NITRR. It achieves an ammonia yield
Rh coordination number >0) with oxidized Rh species (with rate about 11 times higher than that of Rh NPs and a faradic
Rh−Rh coordination number = 0), and (ii) the presence of efficiency of 95% at 0.2 V vs RHE, and the overpotential
low-coordination sites in metallic Rh phase. At the same time, matches the best among previously reported catalysts. The
we observe that under reaction conditions, the NRh−Rh for Rh XAS results show that Rh NFs have low-coordination Rh. The
NFs slightly increases and reaches ca. 7.4 and 8.3 at 0.2 V vs DFT calculation results show that the low-coordination Rh
RHE for 30 min and −0.1 V vs RHE for another 30 min, atoms are beneficial for NITRR with respect to the high-
respectively. For Rh NPs, the Rh−Rh coordination number is coordination Rh atoms, including enhanced adsorption of
9.2 at −0.1 V vs RHE for 30 min. NO3− ions and better stabilization of reaction intermediates.
Since the obtained coordination numbers from XAS The study of NITRR catalytic activity of low-coordination Rh
describe only averaged values over low-coordination sites on in Rh NFs will provide new insight and expand their potential
the catalyst edge, surface and over fully coordinated sites in the applications in various fields.
catalyst bulk. Therefore, the position of low-coordination Rh in
Rh NFs was further explored by the DFT calculation of various
coordination numbers. We constructed defective Rh(111)
models, using edges to present five-coordinated Rh (Rh5C)
■
*
ASSOCIATED CONTENT
sı Supporting Information

with coordination number CN = 5 (Figures 5 and S22). The The Supporting Information is available free of charge at
simulations of Rh7C, Rh8C, and Rh9C were realized by https://pubs.acs.org/doi/10.1021/acscatal.2c03004.
constructing flat (110), (100), and (111) surfaces. These
Experimental procedures, EDS, XPS, SEM, NMR,
contribute to a reasonable conclusion consistent with the
absolute calibration of ammonium solutions, ECSA,
current reports that low-coordination sites are concentrated at DEMS, electrochemistry performance evaluation, and
the edge and surface of nanosheets in Rh NFs.28−31 The DFT calculation (PDF)
superior NH3 yield rate normalized to ECSA of Rh NFs with
more edge and surface sites relative to Rh NPs (Figure 5a) also
indicates that low-coordination Rh at the edge and surface of
Rh NFs may be the main active sites for the NITRR.
Furthermore, the influence of coordination number on the
■ AUTHOR INFORMATION
Corresponding Author
performance of NITRR was explored by the theoretical study Jingshan Luo − Institute of Photoelectronic Thin Film Devices
of the NITRR reaction pathway over Rh with various and Technology, Solar Energy Research Center, Key
coordination numbers. First, to construct a comprehensive Laboratory of Photoelectronic Thin Film Devices and
description of the reaction mechanism, online differential Technology of Tianjin, Ministry of Education Engineering
electrochemical mass spectrometry (DEMS) was utilized to Research Center of Thin Film Photoelectronic Technology,
detect the intermediate species generated during the NITRR. Nankai University, Tianjin 300350, China; Haihe
Figure 5b,c displays the mass-to-charge ratio (m/z) signals Laboratory of Sustainable Chemical Transformations,
recorded as a function of time while performing the NITRR Tianjin 300192, China; orcid.org/0000-0002-1770-
measurement periodically. NH2 and NH3 corresponding to m/ 7681; Email: [email protected]
z signals at 16 and 17 were detected and tracked. Note that m/ Authors
z signals at 31 and 33 corresponding to NH2OH and HNO
Huimin Liu − Institute of Photoelectronic Thin Film Devices
have no obvious periodic fluctuation peak, implying that the and Technology, Solar Energy Research Center, Key
fracture of the N−O bond is completed before the formation Laboratory of Photoelectronic Thin Film Devices and
of the N−H bond. Trace nitrogen may derive from the Technology of Tianjin, Ministry of Education Engineering
dimerization of desorbed N* (Figure S23). Combined with Research Center of Thin Film Photoelectronic Technology,
DEMS and theoretical study, the reaction pathway of the full Nankai University, Tianjin 300350, China; Haihe
NITRR over Rh catalysts includes NO3− adsorption stage, Laboratory of Sustainable Chemical Transformations,
deoxygenation stage, and hydrogenation stage (Figures S24− Tianjin 300192, China
S27), with free energy profiles presented in Figure 5d,e. As Janis Timoshenko − Department of Interface Science, Fritz-
presented in Figure 5 and Table S4, Rh5C shows notably Haber-Institut der Max-Planck-Gesellschaft, Berlin 14195,
better performance as indicated by the maximum free energy Germany
change, ΔGmax = 0.84 eV for Rh9C and 0.55 eV for Rh5C. Lichen Bai − Department of Interface Science, Fritz-Haber-
From the calculated profiles of free energy in Figure 5e, the Institut der Max-Planck-Gesellschaft, Berlin 14195,
performances of Rh8C and Rh7C are also calculated and Germany; orcid.org/0000-0003-1452-6129
showed the maximum free energy change, ΔGmax = 0.71 and Qinye Li − Department of Chemistry and Biotechnology,
0.64 eV, respectively. Based on these calculations, it is clear Swinburne University of Technology, Hawthorn, VIC 3122,
that a low-coordination site is beneficial for NITRR with Australia
respect to a high-coordination site. As demonstrated in Figure Martina Rüscher − Department of Interface Science, Fritz-
5, Rh5C can particularly stabilize the NO3* intermediate state Haber-Institut der Max-Planck-Gesellschaft, Berlin 14195,
due to its lower adsorption free energy. These results strongly Germany
supported our hypothesis that low-coordination Rh can Chenghua Sun − Department of Chemistry and Biotechnology,
promote NITRR, including enhanced adsorption of NO3− Swinburne University of Technology, Hawthorn, VIC 3122,
and better stabilization of reaction intermediates. Australia; orcid.org/0000-0001-7654-669X
1519 https://doi.org/10.1021/acscatal.2c03004
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Beatriz Roldan Cuenya − Department of Interface Science, (10) Wang, Z.; Young, S. D.; Goldsmith, B. R.; Singh, N. Increasing
Fritz-Haber-Institut der Max-Planck-Gesellschaft, Berlin Electrocatalytic Nitrate Reduction Activity by Controlling Adsorption
14195, Germany; orcid.org/0000-0002-8025-307X through PtRu Alloying. J. Catal. 2021, 395, 143−154.
(11) Richards, D.; Young, S. D.; Goldsmith, B. R.; Singh, N.
Complete contact information is available at: Electrocatalytic Nitrate Reduction on Rhodium Sulfide Compared to
https://pubs.acs.org/10.1021/acscatal.2c03004 Pt and Rh in the Presence of Chloride. Catal. Sci. Technol. 2021, 11,
7331−7346.
Author Contributions (12) Kani, N. C.; Gauthier, J. A.; Prajapati, A.; Edgington, J.;
J.L. and H.L. conceived and designed the project. H.L. Bordawekar, I.; Shields, W.; Shields, M.; Seitz, L. C.; Singh, A. R.;
developed the catalysts, performed the characterizations, Singh, M. R. Solar-driven Electrochemical Synthesis of Ammonia
conducted electrochemical tests, and analyzed the data. J.T., Using Nitrate with 11% Solar-To-Fuel Efficiency at Ambient
M.R., and L.B. performed the XAS experiments and analyzed Conditions. Energy Environ. Sci. 2021, 14, 6349−6359.
(13) Li, J.; Zhang, Y.; Liu, C.; Zheng, L.; Petit, E.; Qi, K.; Zhang, Y.;
the corresponding data under the supervision of B.R.C. C.S.
Wu, H.; Wang, W.; Tiberj, A.; Wang, X.; Chhowalla, M.; Lajaunie, L.;
and Q.L. performed the DFT calculation and analyzed the Yu, R.; Voiry, D. 3.4% solar-to-Ammonia Efficiency from Nitrate
corresponding data. H.L. and J.L. wrote the initial draft. J.L. Using Fe Single Atomic Catalyst Supported on MoS2 Nanosheets.
supervised the project. All authors discussed the results and Adv. Funct. Mater. 2022, 32, No. 2108316.
revised the manuscript and gave approval to the final version of (14) Liu, J. X.; Richards, D.; Singh, N.; Goldsmith, B. R. Activity and
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The authors declare no competing financial interest. (15) Zhao, H.; Chen, X.; Wang, G.; Qiu, Y.; Guo, L. Two-
dimensional Amorphous Nanomaterials: Synthesis and Applications.

■ ACKNOWLEDGMENTS
J.L. acknowledges the funding support by the Tianjin
2D Mater. 2019, 6, No. 032002.
(16) Zhu, W. J.; Zhang, L.; Yang, P. P.; Hu, C. L.; Luo, Z. B.; Chang,
X. X.; Zhao, Z. J.; Gong, J. L. Low-coordinated Edge Sites on
Distinguished Young Scholar Fund (20JCJQJC00260), the Ultrathin Palladium Nanosheets Boost Carbon Dioxide Electro-
Haihe Laboratory of Sustainable Chemical Transformations, reduction Performance. Angew. Chem., Int. Ed. 2018, 57, 11544−
and the “111” project (Grant no. B16027). H.L. acknowledges 11548.
the funding support from the China Postdoctoral Science (17) Stamenkovic, V. R.; Fowler, B.; Mun, B. S.; Wang, G. F.; Ross,
Foundation (grant no. 2022M721701). L.B. acknowledges the P. N.; Lucas, C. A.; Markovic, N. M. Improved oxygen reduction
activity on Pt3Ni(111) via Increased Surface Site Availability. Science
Early Postdoc. Mobility Fellowship (P2ELP2_199800) from
2007, 315, 493−497.
the Swiss National Science Foundation. XAS experiments were (18) Stoerzinger, K. A.; Rao, R. R.; Wang, X. R.; Hong, W. T.;
performed at SuperXAS beamline at the SLS Synchrotron Rouleau, C. M.; Shao, H. Y. The Role of Ru Redox in pH-dependent
Radiation Facility (Villigen, Switzerland) with the collabo- Oxygen Evolution on Rutile Ruthenium Dioxide Surfaces. Chem
ration of the SLS staff. 2017, 2, 668−675.

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■ NOTE ADDED AFTER ASAP PUBLICATION

This paper published online on January 10, 2023, with an error
in the Supporting Information. The corrected version was
reposted on January 11, 2023.

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